Process for the improvement of illuminating oils



E. M. CLARK ,960,203

PROCESS FOR THE IMPROVEMENT OF ILLUMINATING OILS May 22, 1934.

Filed Aug. 31, 1929 EDGAR CLARK 3 WCwwL am UNITED STATES PATENT OFFICE PROCESS FOR THE IMPROVEMENT OF ILLUMINATING OILS Edgar M. Clark, Belle Haven, Greenwich, Comm, assignor to Standard-I. G. Company Application August 31, 1929, Serial No. 389,677

8 Claims. (Cl. 196-24) The present invention relates to an improved temperature in excess of 750 F., While under process for producing burning oils from unrepressure in considerable excess of atmospheric fined oil and more specifically to a process for pressure, say in excess of about 20 atmospheres producing high grade burning oils from inferior but preferably at about 200 atmospheres or higher. raw material heretofore regarded as unsuitable Other cuts from crude oil containing the kerofor production of highest grade burning oil. My sene fractions with or without higher boiling cuts invention will be fully understood from the folsuch as gas oil may also be used as will be unlowing description and the drawing which illus derstood. The preferred temperature range is trates one form of apparatus suitable for my from 750 to about 870 F. It is generally most process. satisfactory to circulate about 8,000 to 16,000 cu.

The drawing is a semi-diagrammatic view in ft. of hydrogen per barrel of oil or higher alsectional elevation of an apparatus constructed though the actual consumption may be much less. according to my invention. The volume of hydrogen should in all cases be Referring to the drawing reference numeral 1 above about 5000 cu. ft. per barrel of oil. When denotes a heating coil arranged in a furnace setthe oil is particularly rich in non-parafiinic hyting 2 and adapted to heat a rapidly flowing drooarbons, it is desirable to operate at the more stream of oil and gas to ahigh temperature. The elevated temperatures and it is also desirable to coil discharges into a reaction chamber 3 which increase pressure and rate of gas recirculation. is constructed to Withstand temperatures of 900 The catalysts used are sulphur resistant; for F. or higher and pressures of several hundred atexample, oxides or sulphides of the sixth group mospheres as well as the corrosive effect of the of the periodic system of elements either alone reactants. The chamber or oven 3 is covered with or in mixtures with each other or other oxides an insulating layer 4 and may be heated in any of the alkali or alkaline earth groups. Other suitable manner such as by electrical means (not oxides such as rare earths, aluminum and the shown) but generally the heat added in coil 1 is like may also be added and the catalyst is prefsufiicient. erably packed in the drum in trays or in lumps The reaction chamber is packed with a suitable as disclosed above. a catalytic material 6, to be disclosed below, ar- The feed rate of the oil is preferably above ranged on trays or grids (not shown) or otherabout .1 volumes of oil per hour per volume of the wise supported so that the incoming material drum and between the limits of .5 to 1.3 volumes passes over or through the catalytic layer before of oil per hour, fed to drum per volume of refinding exit by line '7. actor space, although the feed rate may be with- Hydrogen or a gas rich in free hydrogen is out these limits which are most satisfactory. fOTCed under high Pressure through p pe 3 y The greater the time of contact, in general, the Compressor 9 d thence y branch lines d greater the improvement in the kerosene portion 90 11 respectively into the inlet C011 1 and/O1 of the oil. Part of the oil is generally converted Tectly into reactor The Outgoing mixture of into hydrocarbon gas and distillate of a lower on and hydrogen passes by pipe 7 heat boiling point than the original feed so that it changers 12 and 13 and thence to cooler 14 and is generally the practice to steam distill to the separation drum 15. The oil is removed from the proper flash point say 0 to 0 F. It is 95 drum to Storage (not Shown) by line 16 While gas also desirable to wash the purified oil with alkali gigg z gifig fiiflg g g mz i i gjgfigg gz fg immediately after hydrogen treatment but sulphuric acid treatment is unnecessary. Yield compressed by booster pum 18 and then flows to n exchanger 12 and line 8 by line 19. Fresh oil is 01 80 90% DI the 011 naturally bolhng Wlthm 45 forced through line 20 by pump 21 to exchanger w kfirosfine 1 is q d as a high grade 100 13 and thence by line 22 to heating coil illuminating oil, the remainder being a light oil In the operation of my process a kerosene cut and gas of pmfamnic nature sulphur is reduced which is unsatisfactory for illuminating purposes a the a d p w f the oil is i as d. in due to the presence of a substantial proportion addition to improvements in general burning of non-parafiinic or unsaturated hydrocarbons qualities, color, color stability and the like. In such as olefinic but particularly aromatic hydrocase the oil is not water white after the hydrogen carbons as indicated by sulphuric acid absorptreatment, it may be necessary to distill with or tion, bromine numbers and the like is exposed to without steam to a 2 to 10% bottoms, after an 55 the action of the gas rich in free hydrogen at a alkali wash. The distillate from this rerun oper- I smoke.

ation will be satisfactory if the hydrogen treatment has been properly carried out.

As an example of the operation of my process a naphtha bottoms of the following characteristic and totally unfit for burning oil is treated:

Gravity 39.7 A. B1. Initial boiling point 357 F. Final boiling point 508 F. Sulphur 334% Viscosity 400 Saybolt Thermo. Flash 139 F.

This oil is treated with hydrogen under pressure of 3000 pounds per square inch at 820 F. The feed rate equal to about .63 volumes of oil per hour volume of the catalytic chamber. The catalyst is a mixture of tungsten, zinc and magnesium oxides and is placed in the drum in lump form. The gas rate is about 8,500 cu. ft. per barrel of oil fed. The product recovered was 102.5% by volume of the oil fed. The gas loss is under 2% by weight of oil fed.

The total overhead product gives the following inspection:

Percent sulphur 028% Initial boiling point 170 F. Final boiling point 544 F.

This is then washed with alkali and run for the maximum yield of 335 viscosity refined oil, which had the following characteristics. The yield was about Gravity 44.4 Viscosity 355 Saybolt Thermo. Sulphur .021 Flash 125 F. Abel.

This oil is an excellent burning oil which did not crust the wick and showed little tendency to The candle power is high and it is satisfactory in all respects.

The remaining oil is a naphtha having a gravity of 524 A. P. I. and sulphur content of .012 being about 20% by volume of the oil fed, it is substantially saturated.

While I intend my process to be used in the treatment of oils of the boiling range of kerosene, it is desirable to include some heavier fractions as well which may be converted during the treatment into suitable burning oil fractions hydrogen under pressure in excess of 20 atmospheres at temperature between the approximate limits of 750 and 870 F. for a time suiilcient to produce an appreciable quantity of oils boiling below kerosene but less than 20% of the original fractions of that boiling range, whereby nonparafilnic constituents of the oil are substantially eliminated.

2. Process according to claim 1 in which the volume of hydrogen is in excess of 5,000 cubic feet per barrel of oil treated.

3. Process according to claim 1 in which the oil recovered is Washed with an alkaline agent and re-distilled.

4. Process according to claim 1 in which the oils are treated as described in the presence of a sulphur insensitive catalyst.

5. The process for improving the burning quality of a hydrocarbon oil boiling in the burning oil range by saturation and reduction of the nonparafiinic constituents by destructive hydrogenation which comprises passing such an oil, together with a gas rich in free hydrogen, through a reaction zone maintained at a moderate to low destructive hydrogenation temperature and under pressure in excess of 20 atmospheres at a rate of less than about 13 volumes of oil per volume of reaction space per hour whereby an appreciable quantity of oil boiling below kerosene is formed but sufiiciently rapid to prevent formation of more than about 20% of light oil boiling below the kerosene range.

6. The process of improving the burning quality of a hydrocarbon oil boiling in the burning oil range by saturation and reduction of the nonparafiinic constituents by destructive hydrogenation which comprises passing such an oil, together with a gas rich in free hydrogen through a reaction zone maintained at a moderate to low destructive hydrogenation temperature and under pressure in excess of 20 atmospheres at a rate between .1 and 1.3 volumes of oil per volume of reaction space per hour whereby an appreciable quantity of oil boiling below kerosene is produced but the amount of such low boiling oil is limited to less than 20% of the feed.

7. An improved process for improving the burning quality of kerosene by destructive hydrogenation which comprises passing the oil with a gas rich in free hydrogen through a suitable catalytic zone maintained at a temperature between about 750 and 870 F. while under pressure in excess of 20 atmospheres for a period of time sufilcient for production of an appreciable amount of lower boiling oil by destructive hydrogenation, but insufficient to allow formation of more than about 20% of such light oil boiling below the kerosene range whereby non-paraffinic constituents are substantially eliminated, and cooling the materials out of contact with air.

8. A process of improving the burning quality of kerosene by elimination of non-paraffinic constituents therefrom by destructive hydrogenation which comprises passing such an oil together with a gas rich in free hydrogen through a reaction zone maintained at a moderate to low destructive hydrogenation temperature and under pressure in excess of 20 atmospheres at a rate in excess of .1 volume of oil per volume of reaction space per hour, whereby an appreciable quantity of oil boiling below kerosene is produced but such quantity is limited to less than 20% of the product.

EDGAR M. CLARK. 

